Photo-thermal response gemini information anti-counterfeiting encryption method

Abstract

The invention provides a photo-thermal response gemini information anti-counterfeiting encryption method, and relates to the technical field of photo-thermal response gemini information anti-counterfeiting and encryption, and the photo-thermal response gemini information anti-counterfeiting encryption method comprises the following steps: mixing photo-thermal response functional molecules with a wetting agent, a binder and a solvent according to a certain proportion, and then preparing a film sample with a color changing function on a substrate as a multi-stimulus gemini anti-counterfeiting label; the film sample is heated at a specific temperature, and photochromism and photoluminescence discoloration of the film sample occur under ultraviolet irradiation, so that multi-stimulus gemini information anti-counterfeiting is realized; thermal response photochromism and photoluminescence discoloration are achieved by changing the accumulation form of molecules in the material and adjusting weak interaction among the molecules through the temperature, on the basis, a film sample composed of a plurality of discoloration systems is prepared, different photochromism and photoluminescence discoloration information is displayed at different temperatures, and the photoluminescence discoloration effect is good. And the information can be decrypted only by obtaining color-changing information at different temperatures and a decoding method, so that the anti-counterfeiting capability and the information security can be enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of photothermal response twin information anti-counterfeiting and encryption, and in particular to a photothermal response twin information anti-counterfeiting encryption method. Background Art

[0002] With the development of information technology in recent years, information security issues such as data leakage and forgery have gradually emerged in the private, commercial and military fields. These challenges have brought significant risks to personal safety, financial stability and national security. Existing anti-counterfeiting technologies usually have a single way of obtaining information, which can easily be obtained by attackers, causing major information leakage accidents. Therefore, the development of advanced anti-counterfeiting materials and encryption technologies has become an urgent problem to be solved.

[0003] Photochromic materials have become promising candidate materials for information encryption because they can display different colors in response to external stimuli through reversible isomerization, cyclization or cycloaddition reactions. Among them, triarylethene derivatives have attracted great interest in the scientific community in recent years due to their simple chemical structure, high sensitivity and rapid response. However, most existing triarylethene materials only respond to ultraviolet rays, and this single information acquisition method is not suitable for anti-counterfeiting technology. In order to prevent information theft and forgery, using multiple stimuli as keys for decrypting information has gradually become an effective strategy.

[0004] Thermal activation is a low-cost, easy-to-operate method that can be controlled in situ on large and nanoscale surfaces. At the same time, temperature can change the stacking form of molecules inside the material, regulate weak interactions between molecules, and is expected to achieve reversible photochemical switching under thermal stimulation. In addition, triphenylethylene exhibits aggregation-induced emission activity, which can realize light-controlled dual-channel signals. However, the photofluorescence of triphenylethylene molecules usually only involves the switching of fluorescence intensity. This limitation causes triphenylethylene derivatives to only record a single type of information under different optical modes. In contrast, displaying twin information on different optical channels can significantly increase information storage capacity, enhance anti-counterfeiting technology, and improve encryption security levels. However, independently displaying different information in different optical channels still faces great challenges. Therefore, the present invention proposes a photothermal response twin information anti-counterfeiting encryption method to solve the problems existing in the prior art. Summary of the invention

[0005] In view of the above problems, the purpose of the present invention is to propose a photothermal responsive twin information anti-counterfeiting encryption method, which has the advantages of photochromism and photofluorescence color change triggered by temperature changes, and can display completely different information under different optical conditions, thereby helping to enhance anti-counterfeiting capabilities and information security, and can solve the problems existing in the prior art.

[0006] To achieve the purpose of the present invention, the present invention is implemented by the following technical scheme: a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0007] S1: preparing photothermal responsive functional molecules, wetting agents, linkers, solvents and substrates, mixing the photothermal responsive functional molecules, wetting agents, linkers and solvents according to a preset ratio, preparing a film sample with a color-changing function on the substrate after mixing, and using the film sample as a multi-stimulus twin anti-counterfeiting label;

[0008] S2: heating the film sample under a preset temperature condition, and after heating, causing the film sample to undergo photochromic and photofluorescent color change under ultraviolet light irradiation, and then realizing multi-stimulus twin information anti-counterfeiting by utilizing thermal response photochromic and photofluorescent color change;

[0009] S3: Prepare a film sample composed of multiple color-changing systems as a carrier for information encryption;

[0010] S4: Each film sample will undergo photochromic and photofluorescent color change when heated at a specific temperature, and the photofluorescent color change phenomenon is different, so that the film sample combination presents different states at different temperatures, realizing multi-stimulus twin encryption of information.

[0011] A further improvement is that the photothermal responsive functional molecule is selected from one of the compounds having the following molecular structure:

[0012]

[0013] A further improvement is that the weight ratio of the thermal responsive functional molecules, the wetting agent, the connecting material and the solvent is: 10% to 30%: 5% to 20%: 20% to 35%: 20% to 40%.

[0014] A further improvement is that the wetting agent is glycerin, the solvent is water, the connecting material is a water-based dispersible resin, and the water-based dispersible resin is one of polyurethane resin, acrylic resin and alkyd resin.

[0015] A further improvement is that the substrate is one of paper, film, plastic, glass and fiber cloth, and the thickness of the thin film sample formed on the substrate is 0.6-10 μm.

[0016] A further improvement is that the response light band of the ultraviolet light is 254-365nm.

[0017] A further improvement is that the specific method of preparing the film sample with color-changing function is: patterning is performed using mask printing, and the film is placed in a light-proof environment at room temperature for 10 to 14 hours, wherein the room temperature is 25 to 30°C.

[0018] A further improvement is that in said S4, during decryption, the photochromic information and the photofluorescent color changing information of the film sample combination at different temperatures are recorded, and the recorded information and the document with the decoding rules are combined into an encryption device.

[0019] A further improvement is that in S4, different film samples are arranged in order and combined into a whole, the states of sample color change and non-appearance are respectively corresponded to 0 and 1 combinations and converted into digital numbers using binary system, different states have different numbers, different passwords are obtained by combining the photochromic and photofluorescent color change state information at different temperatures, and different photochromic and photofluorescent color change information at different temperatures are combined according to the decoding document to obtain different password information.

[0020] The beneficial effects of the present invention are as follows: a photothermal response twin information anti-counterfeiting encryption method provided by the present invention utilizes the change in the arrangement of aggregated molecules before and after heating of functional molecules to regulate the intermolecular forces and achieve photochromic and photofluorescent color change. Moreover, at a specific temperature, the technology provided by the present invention can provide different information in the photochromic and photofluorescent color change states. This multi-stimulus twin response label can greatly improve the security level of information and provide a guarantee for the encryption and protection of valuable real information in anti-counterfeiting technology. In addition, the anti-counterfeiting label provided by the present invention has a simple preparation process, low production cost, and good repeatability. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the photothermal responsive twin information anti-counterfeiting encryption label prepared by the present invention.

[0022] Figure 2 This is the photochromic and photofluorescent color change phenomenon of the anti-counterfeiting encryption label of the first embodiment of the present invention under thermal stimulation.

[0023] Figure 3 It is a schematic diagram of the photochromic and photofluorescent color-changing phenomena of the anti-counterfeiting encryption label of the second embodiment of the present invention under thermal stimulation.

[0024] Figure 4 It is a schematic diagram of the photochromic and photofluorescent color-changing phenomena of the anti-counterfeiting encryption label of the third embodiment of the present invention under thermal stimulation.

[0025] Figure 5 It is a schematic diagram of the preparation of the anti-counterfeiting encryption label of the fourth embodiment of the present invention and the photochromic and photofluorescent color-changing phenomena at different temperatures.

[0026] Figure 6 This is a schematic diagram of different passwords obtained by decryption in Example 4 of the present invention.

[0027] Figure 7It is a schematic diagram of the preparation of the anti-counterfeiting encryption label of the fifth embodiment of the present invention and the photochromic and photofluorescent color-changing phenomena at different temperatures.

[0028] Figure 8 It is a schematic diagram of different passwords obtained by decryption in implementation case 5 of the present invention. DETAILED DESCRIPTION

[0029] In order to deepen the understanding of the present invention, the present invention will be further described in detail below in conjunction with examples. The examples are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.

[0030] Embodiment 1

[0031] according to Figure 1 , Figure 2 As shown, this embodiment proposes a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0032] Step 1: Material selection

[0033] The photothermal responsive functional molecule used in this embodiment is 1-(2-(4-bromophenyl)-1-phenylvinyl)benzene, as shown below:

[0034]

[0035] The melting point was 78.7°C and the glass transition temperature was -2.4°C as measured by DSC (differential scanning calorimetry). The decomposition temperature was 323°C as measured by thermogravimetric analysis.

[0036] Step 2: Preparation of anti-counterfeiting labels

[0037] Select paper as the substrate, mix 1-(2-(4-bromophenyl)-1-phenylvinyl)benzene, glycerol, polyurethane resin and water in the ratio of 30%:10%:20%:40% evenly, dip a brush into the mixture, and use a rose-shaped pattern as a mask. That is, the area with color-changing properties is the rose area (such as Figure 1 The thickness is 0.6 μm and it is dried at 30°C in the dark for 10 h.

[0038] Step 3: Authenticity Identification Process

[0039] After the rose pattern was placed on a 78.7℃ hot plate and heated, it changed color under 254nm ultraviolet light, from colorless to orange. At the same time, the fluorescence of the functional molecule changed from the original blue fluorescence to fluorescence quenching. Figure 2 When heated to 78.7°C, it shows an orange rose after being irradiated with ultraviolet light, and the fluorescence is quenched, indicating that it is a true label.

[0040] Embodiment 2

[0041] according to Figure 1 , Figure 3 As shown, this embodiment proposes a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0042] Step 1: Material selection

[0043] The photothermal responsive functional molecule used in this embodiment is 1-bromo-4-(2-(4-bromophenyl)-1-phenylvinyl)benzene, as shown below:

[0044]

[0045] The melting point was 72.4°C and the glass transition temperature was 13.7°C measured by DSC (differential scanning calorimetry). The decomposition temperature was 351°C measured by thermogravimetric analysis.

[0046] Step 2: Preparation of anti-counterfeiting labels

[0047] The film was selected as the substrate, 1-bromo-4-(2-(4-bromophenyl)-1-phenylvinyl)benzene, glycerol, acrylic resin, and water were mixed evenly at a ratio of 25%:15%:25%:35%, and the mixture was dipped into a brush, and the chrysanthemum pattern was used as a mask, that is, the area with color change performance was the chrysanthemum area. The thickness was 10 μm, and it was dried at 25°C in the dark for 14 hours.

[0048] Step 3: Authenticity Identification Process

[0049] After the chrysanthemum pattern was placed on a hot plate at 72.4℃, it changed color under 300nm ultraviolet light, from colorless to orange. At the same time, the fluorescence of the functional molecule changed from the original blue fluorescence to fluorescence quenching. Figure 3 When heated to 72.4°C, it shows an orange chrysanthemum after being irradiated with ultraviolet light, and the fluorescence is quenched, indicating that it is a true label.

[0050] Embodiment 3

[0051] according to Figure 1 , Figure 4 As shown, this embodiment proposes a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0052] Step 1: Material selection

[0053] The photothermal responsive functional molecule used in this embodiment is 1,1,2-tri(4-bromophenyl)ethylene, as shown below:

[0054]

[0055] The melting point was 101.1°C and the glass transition temperature was 30.5°C as measured by DSC (differential scanning calorimetry). The decomposition temperature was 355°C as measured by thermogravimetric analysis.

[0056] Step 2: Preparation of anti-counterfeiting labels

[0057] Plastic was selected as the substrate, 1,1,2-tri(4-bromophenyl)ethylene, glycerol, alkyd resin, and water were mixed evenly at a ratio of 20%:20%:30%:30%, a brush was dipped into the mixture, and a lotus pattern was used as a mask, that is, the area with color-changing properties was the lotus area. The thickness was 5.0 μm, and it was dried at 28°C in the dark for 12 hours.

[0058] Step 3: Authenticity Identification Process

[0059] After the lotus pattern was placed on a hot plate at 101.1℃, it changed color under 365nm ultraviolet light, from colorless to orange. At the same time, the fluorescence of the functional molecule changed from the original blue-purple fluorescence to sky blue fluorescence. Figure 4 When heated to 101.1℃, it shows orange chrysanthemum after being irradiated with ultraviolet light, and the fluorescence changes from blue-purple to sky blue, indicating that it is a genuine label.

[0060] Embodiment 4

[0061] according to Figure 1 , Figure 5 , Figure 6 As shown, this embodiment proposes a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0062] Step 1: Material selection

[0063] The photothermal responsive functional molecules used in Example 1, Example 2 and Example 3 are adopted.

[0064] Step 2: Preparation of information encryption device

[0065] On a glass substrate, a flower was used as a mask template, and the preparation methods of the anti-counterfeiting labels of Implementation Cases 1, 2 and 3 were used. The functional molecules of Implementation Cases 1, 2 and 3 were respectively applied to the flower stems, flowers and leaves of the flower with a brush, each with a thickness of 8.0 μm. The samples were dried at 25°C away from light for 14 h.

[0066] Step 3: Information decryption process

[0067] like Figure 5As shown, the flower pattern is placed on a hot table and heated to 72.4°C. After irradiation with 365nm ultraviolet light, two orange flowers appear on the substrate, and the substrate now displays the pattern of flower stems and leaves through fluorescence. The flower pattern is continued to be heated to 78.7°C on the hot table. After irradiation with ultraviolet light, a pattern of two flowers and flower stems appears on the substrate, while only the pattern of blue-purple flowers and leaves is displayed in the fluorescent state. The hot state is continued to be heated to 101.1°C. After irradiation with ultraviolet light, a complete flower, including flowers, flower stems and leaves, appears on the substrate, while only the pattern of sky blue flowers and leaves is displayed in the fluorescent state. There are 6 pattern states at different temperatures. The combinations of 0 and 1 corresponding to these states can be converted into numbers using binary, and the numbers are different for different states. As the temperature rises, the change process of the pattern is regarded as a code book. Different decoding methods can obtain different codes, thereby completing the encrypted storage of information. Figure 6 shown.

[0068] Embodiment 5

[0069] according to Figure 1 , Figure 7 , Figure 8 As shown, this embodiment proposes a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0070] Step 1: Material selection

[0071] The photothermal responsive functional molecules used in Example 1, Example 2 and Example 3 are adopted.

[0072] Step 2: Preparation of information encryption device

[0073] On a fiber cloth substrate, with four numbers "8888" as a mask template, using the preparation methods of the anti-counterfeiting labels of Example 1, Example 2 and Example 3, a brush was used to dip the functional molecules of Example 1, Example 2 and Example 3, respectively, and applied to different parts of the number "8888", with a thickness of 9.0 μm for each part, and dried at 25°C away from light for 14 hours.

[0074] Step 3: Information decryption process

[0075] like Figure 7As shown, the pattern of the number "8888" is placed on a hot table and heated to 72.4°C. After irradiation with 365nm ultraviolet light, the orange number "7117" appears on the substrate, and the substrate now displays "two 00 two" through fluorescence. The digital pattern is continued to be heated to 78.7°C on the hot table. After irradiation with ultraviolet light, the orange number "3113" appears on the substrate, and the fluorescence shows a bluish-purple combination of numbers and letters "1EE1". The hot state is continued to be heated to 101.1°C. After irradiation with ultraviolet light, the orange number "8888" appears on the substrate, and in the fluorescent state it is displayed as a sky blue "1EE1". There are a total of 6 pattern states at different temperatures, and the 6 different states are encoded as a, b, c, d, e, and f respectively. According to the decoding document, different password information can be obtained, thereby completing the encryption and storage of information, such as Figure 8 shown.

[0076] Embodiment 6

[0077] according to Figure 1 As shown, this embodiment proposes a photothermal response twin information anti-counterfeiting encryption method, comprising the following steps:

[0078] S1: Prepare photothermal responsive functional molecules, wetting agents, binders, solvents and substrates. The photothermal responsive functional molecules are the same as those in Example 1. The wetting agent is glycerol, the solvent is water, and the binder is a water-based dispersible resin. The water-based dispersible resin is one of polyurethane resin, acrylic resin and alkyd resin. The photothermal responsive functional molecules, wetting agents, binders and solvents are mixed according to a preset ratio. The weight ratio of the thermal responsive functional molecules, wetting agents, binders and solvents is 10%: 5%: 35%: 40%. After mixing, a film sample with a color-changing function is prepared on the substrate, and the film sample is used as a multi-stimulus twin anti-counterfeiting label, wherein the substrate is glass, and the thickness of the film sample formed on the substrate is 4.0 μm;

[0079] S2: heating the film sample under a preset temperature condition (72.4°C to 101.1°C, 72.4°C in this embodiment), and after heating, irradiating the film sample with ultraviolet light (the response light band of ultraviolet light is 300nm) to cause photochromism and photofluorescence discoloration, and then realizing multi-stimulus twin information anti-counterfeiting by using thermal response photochromism and photofluorescence discoloration;

[0080] S3: preparing a thin film sample composed of multiple color-changing systems as a carrier of information encryption, wherein a specific method of preparing a single thin film sample is: patterning by mask printing, and placing in a light-proof environment at room temperature for 12 hours, wherein the room temperature is 28°C;

[0081] S4: Each film sample will undergo photochromic and photofluorescent color change when heated at a specific temperature, and the photofluorescent color change phenomenon is different, so that the film sample combination presents different states at different temperatures, realizing multi-stimulus twin encryption of information. In S4, the photochromic information and photofluorescent color change information of the film sample combination at different temperatures are recorded during decryption, and the recorded information and the document with the decoding rules are combined into an encryption device. At the same time, in S4, different film samples are arranged and combined into a whole in sequence, and the states of sample color change appearing and not appearing correspond to 0 and 1 combinations respectively and converted into numbers using binary. Different states have different numbers. Different passwords are obtained by combining the photochromic and photofluorescent color change state information at different temperatures. Different photochromic and photofluorescent color change information at different temperatures are combined according to the decoding document to obtain different password information. Alternatively, the photochromic information and photofluorescent color change information of the film sample at a specific temperature correspond to a, b, c, d, e, and f respectively. Different photochromic and photofluorescent color-changing information at different temperatures are combined according to the decoding document to obtain different password information.

[0082] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited by the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the framework and scope of application of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A photothermal response twin information anti-counterfeiting encryption method, characterized in that: The following steps are involved: S1: preparing photothermal responsive functional molecules, wetting agents, linkers, solvents and substrates, mixing the photothermal responsive functional molecules, wetting agents, linkers and solvents according to a preset ratio, preparing a film sample with a color-changing function on the substrate after mixing, and using the film sample as a multi-stimulus twin anti-counterfeiting label; S2: heating the film sample under a preset temperature condition, and after heating, causing the film sample to undergo photochromic and photofluorescent color change under ultraviolet light irradiation, and then realizing multi-stimulus twin information anti-counterfeiting by utilizing thermal response photochromic and photofluorescent color change; S3: Prepare a film sample composed of multiple color-changing systems as a carrier for information encryption; S4: Each film sample will undergo photochromic and photofluorescent color change when heated at a specific temperature, and the photofluorescent color change phenomenon is different, so that the film sample combination presents different states at different temperatures, realizing multi-stimulus twin encryption of information.

2. A photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: The photothermal responsive functional molecule is one of the compounds having the following molecular structure:

3. A photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: The weight ratio of the thermal responsive functional molecules, the wetting agent, the connecting material and the solvent is: 10% to 30%: 5% to 20%: 20% to 35%: 20% to 40%.

4. A photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: The wetting agent is glycerin, the solvent is water, the connecting material is a water-based dispersible resin, and the water-based dispersible resin is one of polyurethane resin, acrylic resin and alkyd resin.

5. The photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: The substrate is one of paper, film, plastic, glass and fiber cloth, and the thickness of the film sample formed on the substrate is 0.6-10 μm.

6. The photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: The response light band of the ultraviolet light is 254-365nm.

7. The photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: The specific method for preparing the film sample with color-changing function is: patterning is performed using a mask plate printing, and the film is placed in a light-proof environment at room temperature for 10 to 14 hours, wherein the room temperature is 25 to 30°C.

8. The photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: In S4, when decrypting, the photochromic information and the photofluorescent color change information of the film sample combination at different temperatures are recorded, and the recorded information and the document with the decoding rules are combined into an encryption device.

9. The photothermal response twin information anti-counterfeiting encryption method according to claim 1, characterized in that: In the S4, different film samples are arranged and combined into a whole in order, and the states of sample color change and non-appearance are respectively corresponded to 0 and 1 combinations and converted into digital numbers using binary system. Different states have different numbers. Different passwords are obtained by combining the photochromic and photofluorescent color change state information at different temperatures. Different photochromic and photofluorescent color change information at different temperatures are combined according to the decoding document to obtain different password information.

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